CN102093580A - Peroxide crosslinked polyethylene pipe and processing method thereof - Google Patents
Peroxide crosslinked polyethylene pipe and processing method thereof Download PDFInfo
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- CN102093580A CN102093580A CN2009102424483A CN200910242448A CN102093580A CN 102093580 A CN102093580 A CN 102093580A CN 2009102424483 A CN2009102424483 A CN 2009102424483A CN 200910242448 A CN200910242448 A CN 200910242448A CN 102093580 A CN102093580 A CN 102093580A
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- Prior art keywords
- polyethylene
- peroxide
- mixture
- crosslinking
- crosslinked polyethylene
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000004717 peroxide crosslinked polyethylene Substances 0.000 title claims abstract description 10
- 238000003672 processing method Methods 0.000 title 1
- -1 polyethylene Polymers 0.000 claims abstract description 37
- 239000004698 Polyethylene Substances 0.000 claims abstract description 33
- 229920000573 polyethylene Polymers 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000004132 cross linking Methods 0.000 claims abstract description 19
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract 4
- 239000000203 mixture Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229920003020 cross-linked polyethylene Polymers 0.000 claims description 6
- 239000004703 cross-linked polyethylene Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 150000002978 peroxides Chemical class 0.000 abstract description 4
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 230000002522 swelling effect Effects 0.000 abstract 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000009700 powder processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a peroxide cross-linked polyethylene pipe and a preparation method thereof; the polyethylene pipe comprises 5-6 per thousand of di-tert-butyl peroxide, 3 per thousand of antioxidant and the balance of polyethylene powder according to mass percentage, the average particle size distribution of the polyethylene powder is 200-300 mu m, and the bulk density is 0.35-0.40g/cm3The density is 0.947g/cm3-0.950g/cm3The pipe has a uniform short branched chain structure, and the crosslinking degree of the peroxide crosslinked polyethylene pipe is more than or equal to 80 percent; the polyethylene powder granularity used for crosslinking into pipes does not need subsequent processing and crushing, relatively reasonable distribution is directly achieved, the same or even higher crosslinking degree is achieved in the crosslinking process under the condition of using less peroxide, and the polyethylene pipe has good heat resistance creep property, impact resistance, swelling property and the like.
Description
Technical field:
The present invention relates to a kind of extrusion molding peroxide crosslinked polyethylene tubing and working method thereof.
Background technology:
Polyethylene mixes with superoxide, and under molten state, peroxide breakdown produces free radical, makes between the polyethylene molecule and forms carbon-carbon bond, and a large amount of intermolecular carbon-carbon bonds makes polyethylene become crosslinking structure.In order to form tridimensional network, polyvinyl resin need be heated to produce crosslinked action.Must fully infiltrate superoxide and oxidation inhibitor before the processing, by the plunger tpe extruding machine peroxide crosslinked polyethylene (PEX-a) powder processing be become tubing then.With new LDPE (film grade) and linear low density polyethylene composition is that the tubing that raw material is processed exists many defectives such as heat-resisting creep properties is poor, shock resistance is poor, swelling behavior difference.The crosslinked course of processing requires the size-grade distribution of polyethylene powders to be in specified range, mixes with superoxide and oxidation inhibitor to help this powder, reaches the effect that identical degree of crosslinking is only used less superoxide.
Patent CN1523052A discloses a kind of rotation molding cross-linked polyethylene special material, is linea low density and low-density polyethylene composition.New LDPE (film grade) powder discharging operation easier is big, and the granularity of said composition is bigger, needs follow-up crushing processing process, and irrational size distribution may cause and superoxide, oxidation inhibitor undercompounding, and cross-linking effect is undesirable.
Patent CN200410026533.3 discloses a kind of radiant crosslinked polyethylene tubing, and the polyvinyl resin that is used for crowded pipe is made up of 70%～100% high density polyethylene(HDPE) and 0～30% linear low density polyethylene.Tube extruding machine obtains through the electron rays radiation after being squeezed into pipe, and degree of crosslinking is on the low side, a little less than the tubing degree of deflection resistance.
Summary of the invention:
An object of the present invention is to process a kind of cross-linked polyethylene pipe with the peroxide crosslinking mode, another purpose provides a kind of slurry process and prepares poly method, be used in the polyethylene powders granularity that is cross-linked into pipe and do not need the following process fragmentation, directly reach relatively reasonable distribution, cross-linking process is issued to identical even higher degree of crosslinking in the situation of using less superoxide.
The invention provides a kind of polyethylene raw material method that is used to prepare peroxide crosslinking tubing.Under whipped state, in polymeric kettle, add Ziegler-Natta catalyst, a certain amount of straight chain saturated alkane or straight chain saturated alkane mixture (C
nH
2n+2) (wherein n is 6-8), add aluminum alkyls (AlR then successively
3) (wherein R is that carbon number is the saturated alkyl of 1-4) and catalyzer, when the polymeric kettle temperature rises to 50 ℃, feed ethene and hydrogen, control reaction temperature and reaction pressure.After reaction is finished, cooling discharge, polymer paste obtains polyethylene powders through separating and drying treatment.
Is that 5～6 ‰ di-t-butyl peroxide ether and massfraction are that 3 ‰ oxidation inhibitor mixed 10 minutes with this powder with accounting for total mixture heavy amount mark, is extruded into cross-linked polyethylene pipe by the plunger tpe tube extruding machine under the high temperature.
Polyethylene powders is characterized as, melting index (MI
21.6) be 1～3g/10min, average particle size distribution is 200 μ m～300 μ m, tap density is 0.35～0.40g/cm
3Density is 0.947g/cm
3-0.950g/cm
3, particularly this polyethylene is resin dedicated has a uniform short-chain branch structure
Ethene polymerization process condition and step are as follows:
1) under nitrogen protection, with 0.2～0.5L aluminum alkyls (AlR
3) (wherein R is that carbon number is the saturated alkyl of 1-4) join 1800L straight chain saturated alkane or straight chain saturated alkane mixture (C
nH
2n+2) in (wherein n is 6-8).
2) add the 100-200g Ziegler-Natta catalyst to reaction system.
3) polymeric kettle is warming up to 50 ℃ and stirred 20 minutes.
4) add 45～90mol hydrogen in above-mentioned reaction system, feed the mixture of ethene and propylene then, ethylene pressure is controlled at≤0.9MPa.
4) control reaction temperature is 80～85 ℃, and reaction pressure is controlled at 0.6MPa-1.0MPa.
5) reaction product is filtered and dry, obtain polyethylene powders.
7) be that 5～6 ‰ di-t-butyl peroxide ether and massfraction are that a kind of or its mixture in 3 ‰ oxidation inhibitor bis-phenol phosphorous acid ester, efficient calcium salt or the distearyl pentaerythrityl diphosphite is in mixing in super mixer under the normal temperature 10 minutes with polyethylene powders with accounting for total mixture heavy amount mark.
8) in 100 ℃～245 ℃ scopes, the said mixture material is extruded into cross-linked polyethylene pipe by the plunger tpe tube extruding machine.
The polyethylene powders granularity that is used to be cross-linked into pipe does not need the following process fragmentation, directly reaches relatively reasonable distribution, and cross-linking process is issued to identical even higher degree of crosslinking in the situation of using less superoxide.The heat-resisting creep properties of this polyvinyl piping materials, shock resistance, swelling behavior etc. are good.
Embodiment
Embodiment 1
Under nitrogen protection, 0.2L triethyl aluminum aluminum alkyls is joined in the 1800L hexane, add the 100g Ziegler-Natta catalyst then.Polymeric kettle is warming up to 50 ℃ and stirred 20 minutes.Add 48mol hydrogen in reaction system, feed the mixture of ethene and propylene then, ethylene pressure is controlled at≤0.9MPa, 80 ℃ of control reaction temperature, and when the ethene add-on reaches 520Kg, stopped reaction.Reactant is filtered and drying, obtain polyethylene product 500Kg.Measuring the polyethylene powders mean particle size is 220 μ m, and bulk density is 0.38g/cm
3
With 80Kg polyethylene powders and 480g di-t-butyl peroxide ether and 240g oxidation inhibitor bis-phenol phosphorous acid ester in super mixer, mixing under the normal temperature 10 minutes.
In 120 ℃ of scopes, the said mixture material is extruded into PEX-a tubing by the plunger tpe tube extruding machine.Measuring PEX-a tubing degree of crosslinking is 88%.
Embodiment 2
Under nitrogen protection, 0.2L triethyl aluminum aluminum alkyls is joined in the 1800L straight chain saturated alkane mixture, add the 120g Ziegler-Natta catalyst then.Polymeric kettle is warming up to 50 ℃ and stirred 20 minutes.Add 55mol hydrogen in reaction system, feed the mixture of ethene and propylene then, ethylene pressure is controlled at≤0.9MPa, 83 ℃ of control reaction temperature, and when the ethene add-on reaches 520Kg, stopped reaction.Reactant is filtered and drying, obtain polyethylene product 500Kg.Measuring the polyethylene powders mean particle size is 300 μ m, and bulk density is 0.40g/cm
3
With 80Kg polyethylene powders and 400g di-t-butyl peroxide ether and 240g oxidation inhibitor bis-phenol phosphorous acid ester in super mixer, mixing under the normal temperature 10 minutes.
In 150 ℃ of scopes, the said mixture material is extruded into PEX-a tubing by the plunger tpe tube extruding machine.Measuring PEX-a tubing degree of crosslinking is 80%.
Embodiment 3
Under nitrogen protection, 0.2L triethyl aluminum aluminum alkyls is joined in the 1800L straight chain saturated alkane mixture, add the 120g Ziegler-Natta catalyst then.Polymeric kettle is warming up to 50 ℃ and stirred 20 minutes.Add 64mol hydrogen in reaction system, feed the mixture of ethene and propylene then, ethylene pressure is controlled at≤0.9MPa, 84 ℃ of control reaction temperature, and when the ethene add-on reaches 620Kg, stopped reaction.Reactant is filtered and drying, obtain polyethylene product 600Kg.Measuring the polyethylene powders mean particle size is 260 μ m, and bulk density is 0.38g/cm
3
With 80Kg polyethylene powders and 450g di-t-butyl peroxide ether and 240g oxidation inhibitor distearyl pentaerythrityl diphosphite in super mixer, mixing under the normal temperature 10 minutes.
In 180 ℃ of scopes, the said mixture material is extruded into PEX-a tubing by the plunger tpe tube extruding machine.Measuring PEX-a tubing degree of crosslinking is 85%.
Embodiment 4
Under nitrogen protection, 0.5L triethyl aluminum aluminum alkyls is joined in the 1800L hexane, add the 200g Ziegler-Natta catalyst then.Polymeric kettle is warming up to 50 ℃ and stirred 20 minutes.Add 80mol hydrogen in reaction system, feed the mixture of ethene and propylene then, ethylene pressure is controlled at≤0.9MPa, 83 ℃ of control reaction temperature, and when the ethene add-on reaches 620Kg, stopped reaction.Reactant is filtered and drying, obtain polyethylene product 600Kg.Measuring the polyethylene powders mean particle size is 240 μ m, and bulk density is 0.35g/cm
3
With 80Kg polyethylene powders and 430g di-t-butyl peroxide ether and 240g oxidation inhibitor distearyl pentaerythrityl diphosphite in super mixer, mixing under the normal temperature 10 minutes.
In 200 ℃ of scopes, the said mixture material is extruded into PEX-a tubing by the plunger tpe tube extruding machine.Measuring PEX-a tubing degree of crosslinking is 83%.
Claims (2)
1. the preparation method of a peroxide crosslinked polyethylene tubing is characterized in that:
Its step is as follows:
1) under nitrogen protection, be that the saturated alkyl aluminium of 1-4 joins in the straight chain saturated alkane or straight chain saturated alkane mixture that the 1800L carbon number is 6-8 with 0.2～0.5L carbon number;
2) add the 100-200g Ziegler-Natta catalyst to reaction system;
3) polymeric kettle is warming up to 50 ℃ and stirred 20 minutes;
4) add 45～90mol hydrogen in above-mentioned reaction system, feed ethene and propylene mixtures then, ethylene pressure is controlled at≤0.9MPa;
5) control reaction temperature is 80～85 ℃, and reaction pressure is controlled at 0.6MPa-1.0MPa;
6) reaction product is filtered and dry, obtain polyethylene powders;
7) be that 5～6 ‰ di-t-butyl peroxide ether and massfraction are that a kind of or mixture in 3 ‰ oxidation inhibitor bis-phenol phosphorous acid ester, efficient calcium salt or the distearyl pentaerythrityl diphosphite is in mixing in super mixer under the normal temperature 10 minutes with polyethylene powders with accounting for total mixture heavy amount mark;
8) in 100～245 ℃ of scopes, the said mixture material is extruded into the oxide compound cross-linked polyethylene pipe by the plunger tpe tube extruding machine.
2. peroxide crosslinked polyethylene tubing, it is characterized in that: the polyethylene powders of preparation method's preparation that described polyvinyl piping materials is peroxide crosslinked polyethylene tubing according to claim 1 by the di-t-butyl peroxide ether of 5-6 ‰, 3 ‰ oxidation inhibitor and surplus is by mass percentage formed, the polyethylene powders average particle size distribution is 200 μ m-300 μ m, and bulk density is 0.35-0.40g/cm
3, density is 0.947g/cm
3-0.950g/cm
3, having uniform short-chain branch structure, peroxide crosslinked polyethylene tubing degree of crosslinking is 〉=80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102424483A CN102093580B (en) | 2009-12-11 | 2009-12-11 | peroxide crosslinked polyethylene pipe and processing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102424483A CN102093580B (en) | 2009-12-11 | 2009-12-11 | peroxide crosslinked polyethylene pipe and processing method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102093580A true CN102093580A (en) | 2011-06-15 |
| CN102093580B CN102093580B (en) | 2012-08-08 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098727A (en) * | 2013-04-03 | 2014-10-15 | 中国石油天然气股份有限公司 | High-density polyethylene resin and preparation and application thereof |
| CN107057156A (en) * | 2017-01-05 | 2017-08-18 | 武汉金牛经济发展有限公司 | A kind of chlorine-resistant Peroxide-crosslinked Pe Pipe and preparation method thereof |
| US11091610B2 (en) | 2016-09-02 | 2021-08-17 | Uponor Infra Oy | Method and composition of making polymer products |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100549081C (en) * | 2006-06-29 | 2009-10-14 | 中国石油化工股份有限公司 | A kind of polyethylene crosslinking substance reaches the polypropene composition by its modification |
| CN101161704B (en) * | 2007-09-29 | 2010-04-14 | 中国蓝星（集团）股份有限公司 | Method for improving metallocene polyethylene cross-linking efficiency and optimizing net structure of conjugate |
-
2009
- 2009-12-11 CN CN2009102424483A patent/CN102093580B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098727A (en) * | 2013-04-03 | 2014-10-15 | 中国石油天然气股份有限公司 | High-density polyethylene resin and preparation and application thereof |
| US11091610B2 (en) | 2016-09-02 | 2021-08-17 | Uponor Infra Oy | Method and composition of making polymer products |
| CN107057156A (en) * | 2017-01-05 | 2017-08-18 | 武汉金牛经济发展有限公司 | A kind of chlorine-resistant Peroxide-crosslinked Pe Pipe and preparation method thereof |
| CN107057156B (en) * | 2017-01-05 | 2020-01-07 | 武汉金牛经济发展有限公司 | Chlorine peroxide resistant crosslinked polyethylene pipe and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102093580B (en) | 2012-08-08 |
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